Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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sackground of The Invention
. _
The present invention is directed to a method for re-
generating sulfur dioxide gas scrubbing solutions. More partic-
ularly, the invention is directed to an improvement in the
method of reoxidizin~ metal salts which have been reduced by
sulfur dioxide absorbed in the scrubbing solutions, whereby
the solutions may be recycled and reused for further sulfur
dioxide removal.
A method for removing sulfur dioxide from gas streams,
such as flue gases, by scrubbing with an aqueous solution of a
reducible metal salt, such as ferric sulfate, has previously
been described and claimed in my U.S. Patent No. 4,070,441
issued January 24, 1978. The disclosure of that patent is in-
f`~ corporated herein by reference.
~- An essential feature of the method covered by U.S.
patent 4,070,441 is the regeneration or reoxidation of the re-
duced metal salt formed from the chemical reaction with sulfur
:,. i
dioxide. The regeneration makes it possible to use an initial
charge of the metal salt for a long period of time by repeated
recycling, without the need of discarding any spent charges and
,~ replacing with fresh ones. The regeneration of the metal salt
in Flue Gas Desulfurization (F.G.D.) processes has great eco-
; nomic and environmental advantages over other F.G.D. methods,
especially those using limeand similar materials which require
dumping of the spent scrubbing material and replacement with
fresh material.
According to U.S. Patent 4,070,441, the regeneration
of the scrubbing solution is accomplished by alternating the
flue gas scrubbing with intervals of scrubbing the solution
with air or other oxygen-containing gas, whereby the oxygen
reoxidizes the reduced metal salt to its oriqinal high valence
state. As these scrubbing cycles with flue gas and air are
repeated many times, there is an increase in the sulfuric acid
content of the scrubbing solution due to the oxidation and con-
version of sulfur dioxide to sulfuric acid which becomes dis-
solved in the scrubbing solution.
It has been recognized that the rate of reoxidation
of the reduced metal salt, such as ferrous sulfate, by air is
impeded or slowed considerably as the sulfuric acid concen-
tration of the solution increases. As a result, ~ furic acidbuild u~
presents a very serious obstacle to F.G.D. processes using
- metal salts such as ferric sulfate, and various means of
accelerating the rate of regeneration have been proposed.
In my U.S. Patent No. 4,091,075, issued May 23, 1978,
it is proposed to use aluminum ions to accelerate the rate of
regeneration or reoxidation of the reduced metal salt with air.
The disclosure o~ that patent is incorporated herein by refer-
ence. Nevertheless, the depressing effect of increasing sul-
furic acid content upon the rate of regeneration of the reduced
metal salt by air still remains a serious factor, and more
efficient methods of regeneration are being sought.
A number of other means of accelerating the rate of
regeneration have been tried or proposed, including thermal
acceleration, chemical accelerators and increase of oxygen in
closed systems. Chemical accelerators, aside from their added
expense, also have the disadvantage that their residues re-
maining in the solution will affect the potential subsequent
industrial utilization of the sulfuric acid building up in the
solution. Direct oxidizing agents such as hydrogen peroxide,
ozone, etc., are volatile and can be expelled by heating the
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fluid. However, they are expensive and add complications
to the process, as in the case with the other above described
accelerating means, as well as raising some potentially serious
environmental problems.
; Summary Of The Invention
The above and other problems of the prior art are
alleviated by the present invention wherein the regeneration of
sulfur dioxide scrubbing solutions containing a reduceable
metal salt is accomplished by reoxidizing the reduced metal
salt in the solution by anodic (electrolytic) oxidation. Thus,
it has been found that anodic oxidation of metal salts such as
the oxidation of ferrous sulfate to ferric sulfate, is not ad-
versely affected by increasing the sulfuric acid content of
solutions containing the metal salt.
Advantageously, the regeneration by anodic oxidation
may be carried out either intermittently or continuously,
and without the necessity of shifting the scrubbing solution
from contact with flue gas to contact with air. However, if
desired, the process of the present invention may be combined
with the process of U.S. Patent 4,070,441, and optionally the
process of patent 4,091,075 so that a portion of the scrubbing
~- solution is regenerated by contact with air or other oxygen
containing gas, and a portion of the scrubbing solution is
regenerated by anodic oxidation.
Brief Description Of The Drawing
For the purpose of illustrating the invention, there
is shown in the drawing a form ~hich is presently preferred; it
being understood, however, that this invention is not limited
to the precise arrangements and instrumentalites shown.
The single figure of drawing is a simplified flow chart
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illustrating the method accordinq to the present invention.
etailed Description Of The Preferrre~ Emobdiment
A shown in the drawing, the sulfur dioxide containing
~ gas stream, such as the flue gas from an industrial coal-
; burning facility, is passed into a flue qas scrubber 10 which
contains an aqueous solution of a metal salt which is capable
~- of being reduced from a high valence state to a lower valence
state. The metal salt may be any water soluble salt of a poly-
valent metal which is capable of being reduced by sulfur diox-
ide and capable of being reoxidized by electrolytic or anodic
oxidation. Suitable commercially available salts include the
:, ~
- salts of such metals as iron, manganese, vanadium, etc., but
.,
the salts of iron (ferric salts) are preferred for ecomomic
reaons. Similarly, any suitable anion may be used which will
render the metal salt water soluble, but the sulfates are pre-
ferred due to their compatability with sulfuric acid formed by
absorption of sulfur dioxide.
For ease of discussion, the process of the present
invention will be described hereinafter with specific refer-
ence to the use of ferric sulfate as the metal salt in theaqueous scrubbing solution. However, it should be understood
that other metal salts such as those indicated above and others
can be employed in the process of the present invention in
- essentially the same manner. The scrubbing solution containing
metal salt is preferably slightly acidic, such as by the addi-
tion of sulfuric acid, and typical reactions of the scrubbing
solution with the sulfur dioxide are set forth in column 2 of
U.S. Patent 4,070,441.
When the scrubbing solution in the flue gas scrubber
reaches a predetermined concentration of ferrous sulfate, the
scrubbing solution is removed from the scrubber 10 and trans-
ferred to an electrolytic cell or cells 12 for reoxidation of
the ferrous sulfate to ferric sulfate. The stage at which the
scrubbing solutionis transferred to the electrolytic cells is
variable and will depend upon a number of practical considera-
tions, such as those described at columns 3 and 4 of U.S.
Patent 4,070,441. Alternatively, if continuous or inter-
mittent regeneration of the scrubbing solution are desired, a
portion of the scrubbing solution may be continuously or per-
iodically removed from the flue gas scrubber to the electrolyticcells and then immediately recycled to the flue gas scrubber
afer reoxidation of the ferrous sulfate to ferric sulfate. If
possible, it would be most desirable to incorporate the electro-
lytic cell into the scrubber 10, so that the solution could be
continuously-regenerated without the need of transferring the solu-
tion, or portions thereof, to a separate cell. So far as is pres-
ently known, these considerations are not critical to the
concept of the present invention and therefore will not be des-
cribed in further detail except by reference to U.S. Patents
~o 4,070,441 and 4,091,075.
Anodic or electrocytic oxidation (which terms will be
used interchangeably herein to denote oxidation in an electro-
lytic cell) of ferrous sulfate to ferric sulfate, per se, has
been known for many years. References to such oxidation may be
found, for example, in J.W. Mellor, Comprehensieve Treatise On
Inorganic And Theoretical Chemistry, Longman, Green & Co.,
London-New York-Toronto (1935), Volume 14, pp. 262, 266, 303,
304 and 315. The mechanisms, details and apparatus of anodic
or electrolytic oxidation are well known to chemists of ordin-
ary skill, and need not be explained here indetail except bysuggesting some possible variations which may be used.
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For example, in the electrolytic oxidation of fer-
rous s~lfate, electroly~is can be carried out in at least two
stages. In the first stage, the product formed at the cathode
of the cell would be hydrogen, which could be used as such, if
:..
locally usable, or returned to a boiler as fuel. In the second
' stage, the product formed at the cathode would be electrolytic
iron, for which many applications are available. At the anode,
oxidation would take place in several stages includinq evolu-
tion of oxygen, formation of persulfuric acid, and oxidation
~; 10 of ferrous to ferric ions.
,. . ~
A number of suitable electrolytic cells are commer-
cially available and known in the art for carrying out electro-
- lytic oxidation. Particularly preferred are the so-called
divided or diaphragm cells in which the anolyte and catolyte
are separ~ted. The anodic oxidation may be carried out by
passing the scrubbing solution, which may contain varying
; amounts of ferric sulfate, ferrous sulfate, sulfuric acid and
other gaseous or solid components derived from the flue gas
which has been scrubbed, through single or multiple electro-
lytic cells. The regenerated anolytes may be returned direct-
ly to the reservoir of scrubber 10 while the anolyte chambers
of the cells are refilled with un-regenerated catolyte. Al-
ternatively, the regenerated anolytes may be stored in bulk
before returning them to scrubber 10. Thus, it will be appar-
ent that the electrolytic cells may be adapted for batch,
intermittent or continuous regeneration and recylcing.
Further, since the regeneration of ferric sulfate
solution by anodic oxidation will be an integral part of the
F.G.D. process, it is contemplated that any or all variables
of the anodic oxidation process, such as voltage, current,
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time, cell desiqn or utilization, flow and storage of liquids,
etc. may be controlled by monitoring a variety of factors in
the overall F.G.D. process. Such factors may include ferrous
sulfate or sulfuric acid content o~ the solution, sulfur diox-
ide content of the flue gas, effectiveness of any other regen-
eration methods used simultaneously, or other factors of the
process.
In the latter regard, it will be understood that re-
generation by anodic oxidation according to the present inven-
tion may be the sole means of regeneration or may be used inconnection with other regenerationmeans such as scrubbing with
air, with the various regeneration methods being used either
in tandem or separately on different portions of the recylced
solution.
If desired, the F.G.D. process may include an addi-
tional scrubber 14 following the flue gas scrubber 10 which
contains ferric sulfate solution. Scrubber 14 may advantage-
ously contain an aqueous solution of a basic nitrogen compound
such as urea or guanidine, for the purpose of trapping and
absorbing acid mist and nitrogen containing combustion gas
products which may be carried over by the gas stream exiting
from scrubber 10. The operation and advantages of such a
scrubber 14 are described in more detail in column 4 of U.S.
~ Patent 4,070,441.
- The feasibility of regeneration of ferric sulfate
scrubbing solutions by anodic oxidation according to the pre-
sent invention is demonstrated by the following specific, non-
limiting examples. It will be understood that a wide variety
or currents, voltages and cell designs may be selected for use
in carrying out the present invention, and those used in the
1~16~;~4
following examples are for illustration only are not intended
to limit the choices of apparatus or procedure.
Example l
A series of solutions of ferrous sulfate containing
different concentrations of sulfuric acid were prepared and
subjected to anodic oxidation. In a first series of tests,
; five 20 ml samples containing 2 grams each of ferrous sulfate
heptahydrate (FeS04-7H20) reagent were prepared and concen-
trated sulfuric acid (specific qravity equal 1.84) was added
to each in sufficient amount to yield nominal volume concen-
trations of 5, lO, 20~ 50 and 66% H2SO4, respectively.
The tests were carried out in a divided cell using
a type 304 stainless steel strip as the cathode and a carbon
rod as the anode with a bridge of electrolyte to convey the
current between catolyte and anolyte. Electrolysis was carried
out with a dc power supply set at 30 volts with a current be-
~ tween 0.1 and 0.3 amperes. After 5 minutes of electrolysis
;~ for each sample, the current was interrupted and a sample of
of the anolyte was withdrawn and the ferric ion content was
qualitatively estimated in comparison to the catolyte by
testing with the well known ammonium thiocyanate reagent.
In each case, there was distinct oxidation (forma-
tion of ferric ions) of the anolyte, as indicated by both the
ammonium thiocyanate test and the visible change of color of
the anolyte toward a yellowish shade. At the highest acid con-
centration (approximately 66~), there was a permanent whitish
turbidity of the solution, indicating the precipitation of a
solid phase from the iron solution.
Example II
Similar tests to Example I were carried out with a
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series of solutions containing 20, 30 and 40 grams, respective-
ly, of ferrous sulfate heptahydrate per 100 ml of water and
various concentrations of sulfuric acid. The samples were
heated to improve solubility. In addition, some of the solu-
tions, instead of being prepared from ferrous sulfate reagent,
were prepared by reaction of ferric sulfate solution with sulfur
dioxide, and contained various proportions of
unreacted ferric sulfate. As with ~xample I, anodic oxidation
of each sample showed an increase in the ferric ion content.
Example III
To a solution containing 10 grams of ferrous sulfate
heptahydrate and sufficient distilled water to yield a total
volume of 100 ml was added 10 ml of concentrated sulfuric acid.
5 ml of the above solution was placed in each of 2 small cas-
seroles, to each of which was added 5 ml concentrated sulfuric
acld, giving a nominal sulfuric acid content of 50 volume per-
cent.
The 2 above casseroles were connected by a salt bridge
consisting of an inverted glass U-tube filled with the initial-
ly prepared acidified ferrous sulfate solution. A stainlesssteel cathode was placed in one casserole, a carbon rod anode im-
mersed in the other to form an electrolytic cell. Using a 30
volt power supply, dc current at 0.1 ampere was passed through
the electrolytic cell.
The anolyte around the carbon anode assumed a brown-
ish or yellowish color in comparison with the catolyte around
the stainless steel cathode, indicating anodic oxidation of the
ferrous sulfate in the anolyte. Testing with ammonium thio-
:
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cyanate solution a samp]e of the anolyte showed an intensiveferric ion color as co~ared with a very faint rose color of
the catolyte.
The above examples indicate that regeneration of fer-
rous sulfate to ferric sulfate by anodic oxidation seems to
proceed independently of the sulfuric acid content of the solu-
tion up to the highest acid concentrations tested. Hence, the
present invention provides considerable advantages over the
prior art oxidation with air which is impeded by acid con-
centration and p~l limitations. Since the anodic oxidation offerrous sulfate is not limited or impeded by increasing acidity
of the electrolyte, the solution can be allowed to increase in
sulfuric acid concentration to levels consistent with efficient
operation of the flue gas scrubber for ecomonic recovery of
sulfuric acid as an ultimate by-product.
In addition to allowing regeneration of ferrous sul-
fate to ferric sulfate over a wide range of acid concentra-
tions, the electric energy requirements for operating electro-
lytic cells used in anodic operation may be considerably less
than the power requirements for pumps, blowers and related
equipment needed for oxidation by air scrubbing. Still fur-
ther advantages of the present method include the smaller space
requirements of electrolytic cells and their accesories as
compared to the requirements for blowers, scrubbing chambers
and related equipment for air oxidation. These advantages make
the present process particularly attractive for small boiler
installations. Also, as previously alluded to, the present
process allows automation of the regeneration procedure based
upon ferrous sulfate content of the solution, sulfur dioxide
content of the flue gas and other process variables.
--10--
s
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The present invention may be embodied in other spe-
cific forms without departinq from the spirit or essential
attributes thereof and, accordingly, reference should be made
to the appended claims, rather than to the foregoing specifi-
cation, as indicating the scope of the invention.
